Purification of butadiene by removing it from oxygen with an absorbent oil



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Sept. 22, 1959 PURIFICATION OF BUTAIE S. C FAUSKE OXYGEN WITH AN ABSORBENT OIL Filed April 4. 1955 NE BY REMOVING IT FROM ATTORNEYS PURIFICATION OF BUTADIENE BY REMOVING IT FROM OXYGEN WITH AN ABSORBENT OIL Sig C. Fauske, Borger, Tex., assigner to Phillips Petroleum Company, a-corporation Aof Delaware Application April 4, 1955, Serial No. 498,950 Claims. (C1. 26o-681.5)

This invention relates to the purication of butadiene.

In one aspect it relates to the purification of free oxygen Contaminated butadiene by removal of the dissolved free oxygen. In another aspect, it relates to the purification of butadiene containing a minor proportion of styrene by removing contaminating atmospheric oxygen. In the copolymerization of butadiene and styrene to produce a synthetic elastomer, commonly called vGR-S synthetic rubber, unreacted butadiene and styrene are usually present in the latex. This condition exists whether employing the cold rubber polymerization process or an older higher temperature copolymerization process. When utilizing either of these processes for the productioncf this 'GR-'S rubber the portions of the butadiene and styrene not converted in the polymerization reacf tion are recovered from the reaction mixture usually by vacuum recovery. As is well known in vacuum processes it is very difcult to exclude all traces of atmospheric Oxygen and thisbutadiene and styrene recovery operation is no exception. Because the contaminating oxygen originates' :from the atmosphere, the oxygen contaminated materials usually also contains free nitrogen. v

It has `been found that oxygen dissolved in .butadiene and/or styrene markedly aiiects the rate of copolymerization of these materials. VIt has alsobeen found that varying concentrations of dissolved oxygen in butadiene and/or styrene cause `the rates of copolymerization to Vary. Thus, it is -dicult to determine Whether a batch of butadiene :and styrene will copolymerize at the normally expected rate or will copolymerize more rapidly or more slowly than the desired rate. When rates of reaction vary lit is difficult to control the temperature of the. reaction. The copolymerization reactionis exothermic and too rapid a rate of reaction tends to increase the temperature of the reactants. In the lproduction `of cold rubber it is very important to maintain Athe temperature of the ,copolymer-ization reaction within relatively .narrow limits.

'In vacuum recovered unreacted'butadiene and styrene concentrations of oxygen as great as l0() or more parts per mililion have been found. When these reactants as recovered containing such a high concentration of dissolved oxygen are blended with newly p-roduced butadiene containing substantially no dissolved oxygen the mixture usually .contains too great a concentration ofjoxygen for proper vplant control of the copolymerization reaction. Thus, it-is highly advantageous to maintain the recovered butadiene-containing a minor -amount -of styrene with as low an oxygen content as possible.

In this specification and claims I use the term butadiene to include 'butadiene containing a minor proportion of styrene. In the above mentioned operation for production of GR-S rubber the vaporous butadiene which contains the contaminating oxygen usually contains about vl to 11/z% styrene. Thus, I use the term butadiene in this specification and claims to mean substantially butadiene that is, `butadiene containing about l to 11/2 styrene.

Drie method of maintaining a low lconcentration of dis- United States Patent i 1 ice solved oxygen in recovered butadiene involves treatment of the recovered liquid butadiene with tertiarybutyl catechol, known as TBC. This method, howevenis quite expensive. It is preferable to provide a processfor preventing oxygen from Abeing vpresent in the liquid butadiene rather than allowing the oxygen to dissolve therein .and then treating the liquid for its removal.

One method heretofore employed involves .passage of vacuum recovered butadiene into a receiving tank. Upon continued passage of the butadiene into this tank the liquid increases in oxygen content to ysuch an extent that the entire recovered liquid has to be treated yfor oxygen removal by such a method as :that mentioned above.

I have found that by continuously removing vaporous butadiene yfrom the butadiene recovery storage tank, .and from the latex purication step and treating ythese vapors for removal of oxygen that the concentration of dissolved oxygen in .the liquid contents or the tank remains relatively small. .In fact, the concentration of oxygen in .the liquid is sufficiently low that thisrecovered liquid can be easily blended oit with newly produced butadiene for use in the copolymerization reaction. The dissolved oxygen content in the blend has been found :to be suciently low that it does not adversely atleet-.the .rate vof the copo1ymerization reaction. p

vAn object of my invention .is to :provide a methodfor recovering unreacted butadiene with a low oxygen com tent.

Another .object ofmy invention .is .toprovlidea method for removing contaminating .oxygen from recycle Ibutediene so that .the finally .recovered Ibutadiene @can .be blended with current butadieneproduction so .that the blend will contain such a small .proportion :of .oxygen `.as not to adverselyaffect .the subsequent pcopolyrnerization of butadiene and styrene.

`Still another object of my invention is to .provide suchk a purication process which can be continuously .operated without `the consumptionofchemicals.

Still another object of my invention .is `to providesuch a `process which .is relatively inexpensive .tooperatefand the .equipment for which Ais relatively inexpensive@ .conf struct and .to maintain.

Still other objects .and advantages -ofniy 'invention be realized .upon reading the following' description, which taken with the .attached drawing, respectivelyv describes and illustrates a preferred embodimentof my invention.

vIn the drawing, the figure illustrates in .diagrammatic form -an `arrangement of apparatus parts `for carrying Aout the processofmyinventio .I accomplish these .and related .objects .by .contacting vaporous'butadiene containing said impurity, that is dis-v solved .free oxygen, with van absorbent .liquid inv ,an ab- -sorption zone, withdrawing absorbent .liquid containing dissolved ,butadiene -from Ysaid zone, flashing the .dissolved butadiene from said absorbent, recovering .the .butadiene from the dashing .operationand removing .gas

purity fromy the .absorption zone..

..I lfurther accomplished fthese...and related objects by.. providing .a method .for :purifying .a .dioleinic hydrot'zar-Y bon .containing freeoxygen gas .asan impurity ,comprising contacting vaporous dioleiinic hydrocarbon .containing saidimpurity with an .absorbentliquid whereby `the hydro-.l carbon is absorbed, removing unabsorbed gas impurity. from the operation, flashing the absorbed ,hydrocarbon from ,the rich .absorbent .liquid and .recovering .the flashed hydrocarbon as the main product of the process.-

I still vfurther accomplished these and related objects by providing amethod vfor purifying an easilyvaporiza'ble hydrocarbon containing free oxygen gas as an impurityl` comprising contacting vapors of said hydrocarbon con# taining said oxygengas with an labsorbent liquid whereby/f the hydrocarbon is absorbed, vremoving unabsorbed: gas

separatorvapors vare withdrawn through lines 10, `11

and 12 under inuence'of avacuum pump 13. pumped material is at least partiallycondensed in Ia condenser 14 and the condensed and'uncondensed materials are passed into a separator 15. From this separator Vaporous material is withdrawn through ai pipe 16 and u ispassed into an absorber 17 in which it is contacted with a mineral seal absorption oil.' Enriched absorption oil is removed from' the 'absorberand is' passed through a line 19' and -through a pressure reduction valve 20 into 'at flash tank 21. From'this tank partially depleted absorption oil iswithdravvn and passed by way of a pipe l 22' and a pressure reduction valve 23 into a second ash tank 24. Fully ashed absorption oil is Withdrawn from this latter tank through a pipe 25 and is transferred by means of pump 26 Ithrough a pipe'44 into the upper portion'of the absorption vessel 17 to complete the mineral seal oil cycle.

The liquid separated from vapor in the separator tank 2 is passed therefrom by way of a pipe 3 into a surge tank 4; From `this tank separated liquid is withdrawn lthrough a pipe and is passed into a'stripp'er 6. In this stripper a small amount of steam is introducedgby way of a pipel 40 for removing final traces of unreacted styrene and any butadiene not separated in separator' 2. Latex free from unreacted hydrocarbon is removed from stripper 6 through a pipe 7 for such disposal or subsequent use as desired.4 yOverhead Vaporous material from stripperl 6' is passed kthrough a pipe 8 to a condenser 37 whichcondenses substantially all of the styrene. This condensed material and any uncondensed material from condenser 37 are passed into a separatorv 39. y The condensate or liquid styrene is removed from separator 39 through a pipe 41 for subsequent use as desired. Vapors from separator 39 are removed by way of a pipe 43 The and are ycombined with Vaporous material from surge tank densed in condenser 37. Condensate is separated in sepseparated in separator 15 is removed from this separator by way of a pipe 31 and is passed into a storage tank 32. Vaporous material from storage tank 32 is removed through pipe 36 and is combined with the aforementioned Vaporous material from pipe 30 and this combined stream of vvapors is further combined with vapors owing through pipe 10. All of these vapors, as combined, flow on through pipe 11 and pipe 12 to follow a course of ow as set forth above. 4 y

Reference numeral 33 identies the Vaporous butadiene in storage tank 32 while reference numeral '.34 identies the butadiene liquid'phase in this tank. This liquid is withdrawn by way of a pipe 35 for such disposal as desired. .Vaporous material from flash tank21 is passed by way of a pipe 27 and is combined with vapors;

enteringppe 12 from pipe 11. Vaporous material hom tank 24 is passed through a pipe 28j Vand is .combined with vapors from pipe 29 prior to passage into the vacuum pump 42.` f

A pipe 18 conducts unabsorbed gaseous materials vfrom the top of the absorber 17 to such disposal asdesired. In order to absorb the butadiene from the vapors fed to Ithe absorber, I operate this mineral seal oil `absorber at a Ypressure from about 25-60 'p.s.i.g.` Rich absorbent oil at this pressure is passed through line 19 and on passing through the pressure reduction valve v20.pres.

Sure 0n this Qil Stream is reduced to about 3 p.s.i.g.' By

this reduction of pressure a considerable proportion of the absorbed butadiene is evolved from the mineral seal oil and as mentioned above this evolved material is passed through line 27 for condensing in condenser 14. The butadiene which is condensed in condenser 14 is separated as a liquid phase in separator 15 and this separated liquid butadiene is passed through pipe 31 to a storage tank 32 and this liquid material is the finished and puri- -fed butadiene product of the process. A A

Absorption oil removed by way of pipe 22 from ash tank 21 still contains an appreciable proportion of butadiene and the pressure on this partially 4depleted absorbent is reduced still further in passing through valve 23 to about 50 millimeters of mercury absolute. This relatively low pressure in ilash tank 24 is maintained by the action of the vacuum pump 42. At this relatively low pressure substantially all of the butadiene is flashed from the absorption oil and the depleted absorbent passes through pipe 25 and is pumped by pump 26 through pipe 44 vfor reintroduction into the absorber 17. In this mannerv I am able to absorb the butadiene from the oxygen'and nitrogen contained in the feed to the absorber without' the consumption of chemicals. Absorbent liquid required the operation as starting absorbent and as makeup absorbent is introduced into the system from a source, not shown, through a pipe 38.

The pressure of about 3 p.s.i.g. maintained'in' ash tank 21 is produced by the action of pump 13 communieating with pipe 12.

I have found by separating vapor from liquid in separater tank 2 which also is maintained under about 3 p.s.i.g. by pump 13 that substantially all of the butadiene is separated from the latex. To make certain all ofthe butadiene is removed from the latex itis exposed to the absolute pressure of about 50 millimetersl of mercury' in the surge tank 4 and this lovv pressure is maintained thereinby the action of the vacuum pump 42L By lthe time the latex leaves the surge tank 4 it is for all practical purposes free from butadiene but it still contains an amount of styrene. In stripper vessel 6 a very small amount of live steam is used as a stripping agent for removal of the styrene. In stripper 6 the recoverable styrene is removed and passed through pipe 8 and conarator 39 and this condensate is substantially pure styrene butadiene-styrene copolymerization operation.

when -added to the butadiene passing from pipe 10 to pipe 11 adds from about 1 to 11/2 percent styrene to the'y In this manner the nal butadiene product butadiene. removed from storage tank 32 contains about 1 to 1% percent styrene by weight.

The following tabulation sets forth the operating conditions of temperature fand pressure maintained in various'l parts of the system:

I have found that in operating such an oxygen (and nitrogen) separating system that liquid butadiene removed from tank 32 contains approximately 10 parts of dissolved oxygen per million While the incomingbutaldiene from the vacuum recovery system in pipe -10 contained about parts per million. When recovered lsubstantially no oxygen, the final blend contains lless than 4 parts per million of dissolved oxygen. Butadiene 'containing less than 4 parts per 'million/of oxygen has little to no effect upon the rate of copolymerizationuof butadiene 4and styrene'even when po1ymerized`atf40 `and lower to form .the- Iso-called `cold rubber.

By the term mineral seal oil I Amean the conventional type of relatively :high boiling straight v-run petroleum `'oil which frequently has a molecular weight in 'the range of labout 200. However other oils can be used as the absorption oil of `my process but -the oilish'ould .be capable of selectively absorbing butadiene from ratmospheric oxygen and nitrogen and the oil must also possess a sufliciently low vapor pressure at absorber temperatures that absorp- 'tion oil vapors will not be lostinthe waste gases. Similarly, vthe k'absorption oil should possess. a Ysufficiently llow partial pressure at flash vpressures that the oil will .not be carried overhead with the butadiene.

I havedescribed herein the operation of my purificaltion process as applied to the vpurification of butadiene. I have selected butadiene merely as an example of the principles involved, but the process is equally applicable for the purification of other diolefinic compounds such as pentadiene, isoprene, chloroprene, piperylene, methylpentadiene, 2,3-dimethyl-1,3-butadiene, and such other hydrocarbons from which it is desired to remove free oxygen.

Such auxiliary apparatus as pressure, and temperature indicating, recording and vcontrolling equipment, many valves and the like, are not illustrated in the drawing nor disclosed for simplicity and brevity purposes. The need lfor such apparatus, its installation and operation are well understood by those skilled in the art.

While mineral seal oil has been herein disclosed as theabsorbent, its use was described merely as an example of a suitable absorbent. Other absorbents, such as furfural, hydrocarbons lower boiling than mineral seal oil can also be used. It is merely necessary that the absorbent be non-corrosive to equipment, non-reactive chemically with materials in process, possess sufficient selective solvent power for the hydrocarbon over the components of air and possess such vapor pressure and/or partial pressure characteristics as not to be lost in the eflluent gases from the absorber and not to be carried overhead from the flashing tanks with the hydrocarbon being purified.

While the above flow diagram has been described for illustrative purposes the invention obviously is not limited thereto.

I claim:

1. A method for removing free oxygen from an admixture with butadiene comprising contacting vaporous butadiene feed stock containing free oxygen impurity with an absorbent mineral seal oil in a vapor-liquid absorption zone maintained at a super-atmospheric pressure, withdrawing absorbent mineral seal oil containing dissolved butadiene, reducing the pressure of the withdrawn mineral seal oil containing dissolved butadiene in a first flashing operation, withdrawing flashed butadiene from said first flashing operation, further reducing the pressure on the absorbent mineral seal oil from the first flashing operation to a sub-atrnospheric pressure in a second flashing operation, removing absorbent mineral seal oil from this second flashing operation and returning same to the absorption operation, removing flashed butadiene from the second flashing operation and combining same with the butadiene from the first flashing operation and with the feed stock vaporous butadiene, at least partially condensing this combined butadiene and removing butadiene condensate as the product of the process and passing the uncondensed butadiene to the above mentioned absorption operation.

I2. The method of `'claim 1 wherein :the absorption l"operation is carried out yat la super-'atmospheric pressure "between approximately 25 and 60 v.p.s;i.g., .andthe first and second 'flashing operations are carried out at about 3 ip.s.i.'g. and '50 .millimeters mercury absolute respectively. 4

3. The method of claim 1 wherein Athe absorption pressure,

-operation is 'carried out -at ;a `temperature between the approximate limits of 50 F. and 100 F.

4. In the method ofclaim ;1, `further separating vaporous butadiene from thelast mentioned butadiene. con- `vdensate, Ycombining these last separated vapors withthe vaporous butadiene feed stock, and recovering liquid 'by weight.

6. A ymethod yfor removing free 'oxygen from an iadmixture ywith lbutadiene comprising contacting vaporous `:butadiene feed stock vcontaining free oxygen impurity with :an absorbent mineral seal oil in a vapor-liquid `absorption zone maintained at a super-atmospheric pressu're, withdrawing absorbent mineral lseal oil containing dissolved butadiene, reducing the pressure of the withdrawn mineral seal oil containing dissolved butadiene in a first flashing operation, withdrawing flashed butadiene from said first flashing operation, further reducing the pressure on the absorbent mineral seal oil from the first flashing operation to a sub-atmospheric pressure in a second flashing operation, removing flashed mineral seal oil from the second flashing operation and returning same to the absorption operation, removing flashed butadiene from the `second flashing operation and combining same with the butadiene from the first flashing operation and with the feed stock vaporous butadiene, at least partially condensing this combined butadiene and removing butadiene condensate to a-storage zone as the product of the process, withdrawing butadiene vapor containing free oxygen impurity from said storage zone, and passing the withdrawn butadiene vapor and the uncondensed butadiene to the abovementioned absorption operation.

7. In the method of claim 1, further separating vaporous butadiene from the last mentioned butadiene condensate at a pressure of from about 15 ,to 30 p.s.i.g. combining this last separated vaporous butadiene with the vaporous butadiene feed stock, and recovering liquidbutadiene of a reduced oxygen content from the latter separating operation as -the product of the process.

8. A method for removing free oxygen from a vaporous feed stock admixture of free oxygen with a diolefinic cornpound selected from the group consisting of butadiene, pentadiene, isoprene, chloroprene, piperylene, methylpentadiene and 2,3dimethyl1,3butadiene comprising contacting said admixture with an absorbent mineral seal oil in a vapor-liquid absorption zone maintained at a super-atmospheric pressure, withdrawing absorbent mineral seal oil containing said diolefinic compound, reducing the pressure of the Withdrawn mineral seal oil containing dissolved diolefinic compound in a first flashing operation, withdrawing flashed diolefinic compound from said first flashing operation, further reducing the pressure on the absorbent mineral seal oil from the first flashing operation to a subatmospheric pressure in a second flashing operation, removing absorbent mineral seal oil from this second flashing operation and returning same to the absorption operation, removing flashed diolefinic compound from the second flashing operation and combining same with the diolefinic compound from the first flashing operation and with the feed stock diolefinic compound, at least partially condensing those combined diolefinic materials and removing diolefnic compound condensate as the product of the process and passing vapors remaining from the partial condensing operation to the above mentioned absorption step.

9.' ln the method of claim 8, further continuously sep- :arating vapors of said diolenic `compound from the .last

mentioned condensate, combining these last separated vap'ors with. the'. rst mentioned kvaporous admixture, 'and `recovering liquid dioletinic compound of reduced oxygen content from the further continuous separation opera- -tion as the product of the process. 1 t Y .10. A method for removing free oxygen from ann. admixture with Abutadiene Vcomprising contacting a rst -vaporous butadienelfeed stock containing free oxygen :drawing flashed butadiene from said tirst flashing operation, further reducing the pressure on the absorbent min- -eral seal oil from. the first flashing operation to a vsubatmosphericlpressure in a second ashing operation, removing flashed mineral seal oii from the second flashing operation and returning same to the absorption operation lasv the iirst mentioned Vabsorbent mineral seal oil, remov- .ing ashed butadiene from the second ashing operation o and combining same with a second vaporous butadiene feedstock containing free oxygen impurity and .with the butadiene from the tirst flashing operation, at least partially condensing this combined butadiene and removing butadiene condensate to a storage zone as the product of the process, continuously withdrawingbutadiene'vapor ,containing free oxygen impurity from said storage zone, .passing this withdrawn butadiene vapor with the butadiene combined from' the first and secondashing steps and second feed stock to the partial condensing step, and the uncondensed butadiene from the partial condensing step being said rst lvaporous butadiene feed stock.

References Cited inthe ie of this patent UNITED STATES PATENTS 1,958,553 Van Nuys May 15, 1934 2,376,425 .Frey May 22,1945 A 2,386,310. Hachrnuth Oct. 9, 1945 2,600,133 -Simms June 10, 1952 2,631,175 Crouch ..-A Mar. 10, 1953 2,689,624 Davis Sept. 21, 1954 n 2,765,8.72 Hartman et al. Oct. 9, 1956 

1. A METHOD FOR REMOVING FREE OXYGEN FROM AN ADMIXTURE WITH BUTADIENE COMPRISING CONTACTING VAPOROUS BUTADIENE FEED STOCK CONTAINING FREE OXYGEN IMPURITY WITH AN ABSORBENT MINERAL SEAL OIL IN A VAPOR-LIQUID ABSORPTION ZONE MAINTAINED AT A SUPER-ATMOSPHERIC PRESSURE, WITHDRAWING ABSORBENT MINERAL SEAL OIL CONTAINING DISSOLVED BUTADIENE, REDUCING THE PRESSURE OF THE WITHDRAWN MINERAL SEAL OIL CONTAINING DISSOLVED BUTADIENE IN A FIRST FLASHING OPERATION, WITHDRAWING FLASHED BUTADIENE FROM SAID FIRST FLASHING OPERATION, FURTHER REDUCING THE PRESSURE ON THE ABSORBENT MINERAL SEAL OIL FROM THE FIRST FLASHING OPERATION TO A SUB-ATMOSPHERIC PRESSURE IN A SECOND FLASHING OPERATION, REMOVING FLASHED BUTASEAL OIL FROM THIS SECOND FLASHING OPERATION AND RETURNING SAME TO THE OBSORPTION OPERATION, REMOVING FLASHED BUTADIENE FROM THE SECOND FLASHING OPERATION AND COMBINING SAME WITH THE BUTADIENE FROM THE FIRST FLASHING OPERATION AND WITH THE FEED STOCK VAPOROUS BUTADIENE AT LEAST PARTIALLY CONDENSING THIS COMBINED BUTADIENE AND REMOVING BUTADIENE CONDENSATE AS THE PRODUCT OF THE PROCESS AND PASSING THE UNCONDENSED BUTADIENE TO THE ABOVE MENTION ABSORPTION OPERATION. 